JP6736835B2 - Method for producing gamma-butyrolactone - Google Patents

Description

In the present invention, any one or more compounds selected from succinic acid and/or its derivative (hereinafter, both may be collectively referred to as “succinic acids”) are hydrogenated to obtain gamma-butyrolactone (hereinafter referred to as “GBL”). A) is manufactured. More particularly, it relates to a method for producing GBL in which a specific nitrogen-containing compound is present in a specific concentration in a hydrogenation reaction mixture when hydrogenating succinic acids to produce GBL.

Examples of the succinic acids to which the present invention is applicable include succinic acid, succinic anhydride, and succinic acid ester.
GBL is useful as an industrial solvent, a cleaning agent, a reaction intermediate for polymer chemicals, and is widely used as a solvent and an electrolytic solution in the production of electronic materials. N-methylpyrrolidone (hereinafter referred to as "NMP") It is also used as a raw material for polyvinylpyrrolidone, which is widely used as a water-soluble polymer.

GBL is industrially produced by a hydrogenation reaction of maleic anhydride, which is a petrochemical product, or succinic anhydride obtained by partially hydrogenating it, a dehydrogenation reaction of 1,4-butanediol, and the like. For example, a method is known in which a succinic acid derivative such as succinic anhydride is hydrogenated in the presence of a ruthenium catalyst to obtain GBL (Patent Document 1).
From the viewpoint of the recent skyrocketing prices of petroleum resources and consideration for the environment, the use of biomass as a raw material to replace petroleum resources has attracted attention, and a method for producing a dicarboxylic acid and its derivative by fermentation of sugars contained in the biomass (hereinafter, A method of producing succinic acids by a fermentation method using such biomass as a raw material is abbreviated as “bio method”) has been studied (for example, Patent Document 2). The succinic acid obtained by the bio method may include a nitrogen-containing compound that is present in the biomass, is mixed in in the fermentation step, or is left without being sufficiently removed in the purification step of the succinic acid. (For example, Patent Documents 3 and 4).

Therefore, in the GBL production process using succinic acid as a raw material, the reaction activity may be reduced due to the impurities in the raw material as described above, which causes a problem that the yield of GBL which is a target product becomes unstable. is there.

Japanese Unexamined Patent Publication No. 64-25771 JP, 2010-100617, A U.S. Patent Application Publication No. 2012/0238722 International Publication (WO) 2013/033649

The present invention has been made to solve the above problems. That is, an object of the present invention is to provide a method for stably producing GBL in a high yield in a method for producing gammabutyrolactone (GBL) by hydrogenation of succinic acids, and particularly hydrogenation using a catalyst. In the reaction, it is to suppress fluctuation (decrease) in GBL yield by preventing decrease in catalyst activity. Use of the method of the present invention provides an industrially advantageous process by which GBL can be stably obtained in a high yield.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the nitrogen-containing compound in the raw material has a great influence on the activity and stability of the hydrogenation catalyst, which in turn greatly affects the yield of GBL. Found.
That is, by setting the concentration of the nitrogen-containing compound in the reaction mixture in the hydrogenation reaction within a predetermined range, it is possible to obtain GBL in a high yield and prevent deterioration of the metal catalyst as the hydrogenation catalyst. Then, the present invention was completed.

That is, the gist of the present invention is
[1] A method for producing gamma-butyrolactone by hydrogenating succinic acid and/or its derivative (hereinafter, both may be collectively referred to as “succinic acids”), which is included in the reaction mixture during the hydrogenation reaction. The total content of the nitrogen-containing compounds is 1 mass ppm or more and less than 5000 mass ppm in terms of nitrogen atom, the method for producing gamma-butyrolactone,
[2] A method for producing gamma-butyrolactone by hydrogenating succinic acid and/or its derivative (hereinafter, both may be collectively referred to as “succinic acids”), which is included in the reaction mixture during the hydrogenation reaction. The total content of the nitrogen-containing compounds represented by the general formula (1) having a molecular weight of 1000 or less is 1 mass ppm or more and less than 5000 mass ppm in terms of nitrogen atoms, and the production of gammabutyrolactone according to 1 above. Method,

(In the formula (1), R ^{1 to} R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxy group, an amino group, an alkylthio group, an arylthio group, an alkylcarbonyl group, Or an arylcarbonyl group, which may further have a substituent, and the substituent may contain a hetero atom, R ² and R ³ are bonded to each other to form a ring. In addition, R ^{1 to} R ³ may be the same or different, provided that the total number of carbon atoms of R ^{1 to} R ³ is 50 or less, and R ^{1 to} R ³ are Except when all are hydrogen atoms.)
[3] The total content of the above-mentioned nitrogen-containing compounds in the reaction mixture during the hydrogenation reaction is 5 mass ppm or more and less than 3000 mass ppm in terms of nitrogen atom. A method for producing the gamma-butyrolactone described,
[4] The method for producing gamma-butyrolactone according to any one of the above 1 to 3, wherein the nitrogen-containing compound has a molecular weight of 200 or less.
[5] The hydrogenation reaction is carried out using a catalyst containing at least one metal selected from transition metals belonging to Groups 8 to 11 of the Periodic Table. The method for producing gamma-butyrolactone according to Item,

[6] The method for producing gamma-butyrolactone according to any one of 1 to 5 above, wherein the vapor pressure of the nitrogen-containing compound at room temperature (25° C.) is 1×10 ⁻¹⁰ Pa or more and 1000 Pa or less. ,
[7] The method for producing gamma-butyrolactone according to any one of 1 to 6 above, wherein the hydrogenation reaction is performed using a catalyst containing ruthenium or copper.
[8] The method for producing gamma-butyrolactone according to any one of 1 to 7 above, wherein the hydrogenation reaction is performed using a ruthenium complex having a tertiary organic phosphorus compound as a ligand as a catalyst,
[9] The method for producing gamma-butyrolactone according to any one of 1 to 8 above, wherein the succinic acids are produced by a fermentation method using a biomass raw material.
[10] The succinic acid is succinic acid, the nitrogen-containing compound is at least one compound selected from the group consisting of succinic acid diamide, succinic acid monoamide, and succinimide, and is used for the hydrogenation reaction. 10. The method for producing gamma-butyrolactone according to any one of 1 to 9 above, wherein the catalyst is a ruthenium complex having a tertiary organic phosphorus compound as a ligand.
Exist in.

According to the method of the present invention, when a GBL is produced by hydrogenation of succinic acids, by controlling the type and concentration of the nitrogen-containing compound in the reaction mixture, deterioration of the metal catalyst used as a hydrogenation catalyst can be prevented. It is possible to provide an industrially extremely advantageous process capable of stably producing GBL in a high yield for a long period of time.

1. Reaction raw material 1-1. Succinic Acids As the raw material succinic acids used in the method for producing GBL of the present invention, each compound corresponding to succinic acids may be used alone, or two or more thereof may be used in any amount ratio in combination. Good.

When a succinic acid ester is used as the succinic acid, a linear dialkyl ester having 1 to 4 carbon atoms is preferable, and dimethyl ester and diethyl ester are particularly preferable in terms of availability and reaction results.
As the succinic acids, succinic acid salts (including acidic ester salts) can also be used. Examples of such succinic acid salts include ammonium salts, sodium salts, potassium salts, succinic acid salts such as calcium salts, and acidic succinic acid ester salts. Among them, in terms of reactivity, diammonium succinic acid salts and acidic salts are exemplified. Ammonium succinate salts are preferred.

1-2. Method for producing succinic acids As a method for producing succinic acids used in the present invention, a method using fossil fuel such as petroleum as a raw material (hereinafter, sometimes referred to as “petrification method”) or a fermentation process from biomass resources is used. (Hereinafter, may be referred to as “bio method”). Among them, succinic acids produced by the bio method are preferably used. This is because the succinic acid produced by the bio method contains a nitrogen-containing compound, and by controlling the total concentration of these compounds, an industrially advantageous method for producing GBL can be provided.

Examples of the method for producing succinic acid by the petrochemical method include those obtained by fractionating petroleum by distillation and/or extraction, and hydrocarbons treated by catalytic cracking (for example, fluid catalytic cracking, thermal cracking or hydrocracking). There is a method of using a decomposed product as a raw material. Examples of industrial succinic acid raw materials include C4, C5, and C6 fractions. From these succinic acid raw materials, succinic acids can be directly produced, or succinic acids can be produced via an intermediate. .. Specifically, a method of oxidizing benzene or butane to produce maleic anhydride or maleic acid ester, and then hydrogenating them to produce succinic acids can be exemplified.

In the method for producing succinic acid by the bio method, examples of biomass resources that can be suitably used include, for example, wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, tapiocacas, bagasse, Plant-derived resources such as vegetable oil residue, potatoes, buckwheat, soybeans, fats and oils, waste paper, papermaking residues, marine product residues, animal-derived resources such as livestock excrements, mixed resources such as sewage sludge, food waste, among others, among others. Plant resources are preferred.

Among the plant resources, wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, potato, oil and fat, waste paper, papermaking residue are preferable, and corn, sugar cane, cassava, and sago palm are particularly preferable.
Carbon sources derived from the above biomass resources include hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose; pentoses such as arabinose, xylose, ribose, xylulose and ribulose; maltose, sucrose, lactose and trehalose. , Disaccharides/polysaccharides such as starch, cellulose; butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monoctic acid, Fatty acids such as arachidic acid, eicosenoic acid, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid, cerakolenic acid; glycerol, mannitol, xylitol, ribitol and other fermentable sugars Among these, hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose; pentoses such as arabinose, xylose, ribose, xylulose and ribulose; maltose, sucrose, lactose, trehalose, starch, cellulose and the like 2 Sugars and polysaccharides are preferable, and among these, glucose, maltose, fructose, sucrose, lactose, trehalose and cellulose are preferable.

From the above various carbon sources, succinic acids can be obtained by a fermentation method by microbial conversion using, for example, coryneform bacteria, Bacillus bacteria, Rhizobium bacteria, Mycobacterium bacteria and the like. Coryneform bacteria are preferable as such microorganisms.
The reaction temperature, pressure and other reaction conditions during the conversion of microorganisms by the fermentation method depend on the activity of the selected microorganisms such as fungi and mold, and may be appropriately selected according to the purpose.

2. Nitrogen-containing compound 2-1. Kind of Nitrogen-Containing Compound The nitrogen-containing compound used in the present invention is at least either an amide compound represented by the following general formula (1) and having a molecular weight of 1000 or less, or 2,3,5,6-tetramethylpyrazine.

(In the formula (1), R ¹ and R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, hydroxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, or an aryl represents a carbonyl group, these groups may have a substituent, may contain heteroatoms in the substituents. also, R ¹ and R ³ be the same or different However, the total number of carbon atoms of R ¹ and R ³ is 50 or less, and the case where all of R ¹ and R ³ are hydrogen atoms is excluded R ² is an alkylcarbonyl group or an arylcarbonyl group. These groups may further have a substituent, and the substituent may contain a hetero atom.

R ¹ -C≡N (3)
(Wherein, ^{R 1} has the same meaning as ^{R 1} in formula (1).)

R ¹ -N=C=O (4)
(Wherein, ^{R 1} has the same meaning as ^{R 1} in formula (1).)

The alkyl group is a chain (linear or branched) alkyl group or a cyclic alkyl group, and in the case of a chain alkyl group, the number of carbon atoms is usually 1 to 20 and 1 to 12 Is preferred. Specific examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group and an octyl group. , Decyl group and the like. The number of carbon atoms in the case of a cyclic alkyl group is usually 3 to 20, preferably 4 to 11. Specific examples thereof include a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. The substituent that the alkyl group may have is not particularly limited as long as it does not significantly impair the effects of the present invention, and examples thereof include an aryl group, an acyl group, a hydroxyl group, an alkoxy group, a carboxyl group, and an aryloxy group. , An alkylaryloxy group, an amino group, an aminoalkyl group, a phosphoric acid group, a phosphono group, a phosphino group, a phosphoryl group, a sulfide group and the like, and the formula weight thereof is usually about 200 or less.

The alkenyl group is a chain (linear or branched) alkenyl group or a cyclic alkenyl group, and in the case of a chain alkenyl group, the number of carbon atoms is usually 2-20, preferably 2-12. is there. Specific examples thereof include an ethenyl group, a 1-propenyl group, an isopropenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, a 2-hexenyl group and the like. The number of carbon atoms in the case of a cyclic alkyl group is usually 3 to 20, preferably 4 to 11, and specific examples thereof include a cyclopropenyl group, a cyclopentenyl group, a cyclohexenyl group and the like. As the substituent that the alkenyl group may have, the same substituents as those exemplified for the above alkyl group can be used as long as the effects of the present invention are not significantly impaired.

Examples of the aryl group include a phenyl group, a benzyl group, a mesityl group, a naphthyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, and a 2,4-dimethylphenyl group. Group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, isoxazolyl group, isothiazolyl group, imidazolyl group, oxazolyl group, thiazolyl group, thiadiazolyl group, thienyl group, thiophenyl group, triazolyl group , Tetrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, pyrazolyl group, pyrrolyl group, pyranyl group, furyl group, flazanyl group, imidazolidinyl group, isoquinolyl group, isoindolyl group, indolyl group, quinolyl group, pyridothiazolyl group, benzimidazolyl group Group, a benzoxazolyl group, a benzothiazolyl group, a benzotriazolyl group, a benzofuranyl group, an imidazopyridinyl group, a triazopyridinyl group, a purinyl group and the like, and the carbon number thereof is usually 5 to 20, preferably Is 5-12 and includes heteroaryl groups containing oxygen, nitrogen, sulfur and the like.

The substituent that the aryl group may have is not particularly limited as long as the effects of the present invention are not significantly impaired, but examples thereof include an alkyl group having 1 to 10 carbon atoms, an acyl group having 1 to 10 carbon atoms, and 1 carbon atom. -10 alkoxy group, C1-10 cycloalkyl group, C6-10 aryl group, C6-10 aryloxy group, C7-12 alkylaryl group, C7-12 Examples thereof include an alkylaryloxy group, an arylalkyl group having 7 to 12 carbon atoms, an arylalkoxy group having 7 to 12 carbon atoms, and a hydroxy group. In addition, a hetero atom such as oxygen, nitrogen, sulfur or phosphorus may be contained in this substituent.

The number of carbon atoms in the alkyl group portion of the alkoxy group is usually 1 to 20, preferably 1 to 12. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group and a phenoxy group. As the substituent that the alkoxy group may have, the same substituents as those exemplified for the above alkyl group can be used as long as they do not significantly impair the effects of the present invention.

The amino group has usually 0 to 20 carbon atoms, and preferably 0 to 12 carbon atoms. Specific examples thereof include amino group (-NH2), methylamino group, ethylamino group, propylamino group, butylamino group, dimethylamino group, diethylamino group, anilino group, toluidino group, anisidino group, diphenylamino group, N -Methyl-N-phenylamino group and the like. As the substituent that the amino group may have, the same substituents as those exemplified for the above alkyl group can be used as long as they do not significantly impair the effects of the present invention.

The number of carbon atoms in the alkyl group portion of the alkylthio group is usually 1 to 20, preferably 1 to 12. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group and an isopropylthio group. As the substituent that the alkylthio group may have, the same substituents as those exemplified for the above alkyl group can be used as long as they do not significantly impair the effects of the present invention.

The number of carbon atoms of the aryl group portion of the arylthio group is usually 6 to 20, and preferably 6 to 12. Specific examples of the arylthio group include a phenylthio group and a tolylthio group. As the substituent that the arylthio group may have, the same substituents as those exemplified for the above alkyl group can be used as long as they do not significantly impair the effects of the present invention.

When the alkylcarbonyl group or arylcarbonyl group has a substituent, the alkyl group or aryl group usually has 0 to 20 carbon atoms, and preferably 0 to 12 carbon atoms.
When it has an alkylcarbonyl group or an arylcarbonyl group as a substituent, the compound of formula (1) becomes an alkylamide or arylamide as a whole. Hereinafter, the amide compound will be described.

Amide groups in amide compounds generally have a resonance structure, and unpaired electrons on the nitrogen atom are delocalized by an adjacent carbonyl group, so that amides are generally stable and hydrogenated on succinic acids. It can exist stably even under relatively high temperature conditions such as Further, the primary amide and the secondary amide form a strong hydrogen bond between the molecules and thus have a high boiling point and do not volatilize so much even at a high temperature, so that the concentration of the nitrogen compound in the reaction mixture can be easily controlled.

In addition, when it has two alkylcarbonyl groups and/or arylcarbonyl groups as a substituent of the said nitrogen atom, the compound of Formula (1) will be an imide compound, but the description here includes an imide compound. It is assumed that
In the case of the amide compound and the imide compound, the number of the substituents other than the alkylcarbonyl group or the arylcarbonyl group with respect to the nitrogen atom of the formula (1) is 1 or 2, and the remaining substituents are the above R ^{1 to} R ³ . What is used is used without particular limitation. Preferred substituents are alkyl groups, alkenyl groups or aryl groups.

In the nitrogen-containing compound contained in the reaction mixture of the present invention, any ^one of R ^{1 to} R ³ of the nitrogen-containing compound represented by the formula (1) (first nitrogen-containing compound) is a hydrocarbon. When it is a group, that is, an alkyl group, an alkenyl group, or an aryl group, a divalent hydrocarbon group obtained by removing one hydrogen atom from this group is a second nitrogen-containing compound represented by the above formula (1). The two nitrogen-containing compounds may be bonded to each other to form a third nitrogen-containing compound in a form shared by any ^one of R ^{1 to} R ³ of the above. In this case, the first and second nitrogen-containing compounds having the substituent may be the same or different from each other, and the third nitrogen-containing compound is a single nitrogen-containing compound having the above-mentioned molecular weight and other factors. The conditions regarding the substituents are applied, and all the substituents R ⁿ (R ⁿ is a substituent which the first and second nitrogen-containing compounds have, that is, all of R ^{1 to} R ³ relating to the two compounds are collectively referred to. The total number of carbon atoms is 50 or less, and is excluded when all R ⁿ are hydrogen atoms.

In addition, including the case where two nitrogen-containing compounds represented by the formula (1) are bonded in such a manner that the substituents are shared as described above, the term "nitrogen-containing compound represented by the formula (1)" is collectively referred to as To do.
The imine compound has the formula (2):
R ¹ R ² C=N-R ³ (2)
^(Wherein, R 1 to R ³ have the same meanings as ^R 1 to R ³ in the formula (1).)
It is represented by. Of these, compounds having a pyridine ring, compounds having a pyrazole ring, and compounds having a pyrazine ring are preferable.

The nitrile compound is represented by the formula (3):
R ¹ -C≡N (3)
(Wherein, ^{R 1} has the same meaning as ^{R 1} in formula (1).)
It is represented by.
The isocyanate compound has the formula (4):
R ¹ -N=C=O (4)
(Wherein, ^{R 1} has the same meaning as ^{R 1} in formula (1).)
It is represented by.

2-2. Specific Examples of Nitrogen-Containing Compound The nitrogen-containing compound of the above formula (1) needs to have a molecular weight of 1,000 or less. Those having a molecular weight of more than 1000 generally have large steric hindrance and extremely weakly interact with the hydrogenation catalyst, so that the effects of the present invention cannot be sufficiently obtained. A more preferable molecular weight is 500 or less, further preferably 300 or less, and particularly preferably 200 or less.

Specific examples of the nitrogen-containing compound of the formula (1), for example, A acetamide, N- methylacetamide, N- ethylacetamide, N, N- dimethylacetamide, monoamide of succinic acid, diamide succinic acid, fumaric acid diamide, fumaric Chain skeleton amides such as acid monoamide, malic acid diamide, malic acid monoamide, maleic acid monoamide and maleic acid diamide, aromatic amides such as benzamide, 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, N -Cyclic amides such as vinylpyrrolidone, 2-piperidone and N-methylpiperidone, and imides such as succinimide and N-methylsuccinimide.

These preferred compounds among, co Haq acid diamide, monoamide of succinic acid, fumaric acid diamide, fumaric acid monoamide, malic acid diamide, malic acid monoamide, maleic monoamide, maleic acid diamide, 2-pyrrolidone, N- methylpyrrolidone, succinic Amides such as acid imide and N-methylsuccinimide.

Specific examples of the nitrogen-containing compound of the formula (2) include, for example, imidazole, oxazole, pyridine, pyrazole, pyrimidine, 1-methylimidazole, 4-methylimidazole, methylpyridine, methylpyrimidine, methylpyrazine, 2,3,5. , 6-tetramethylpyrazine, 3,6-dimethylpyridazine, tetramethylpyrazole, 3,6-dimethylpyridazine and the like.

Specific examples of the nitrogen-containing compound of the formula (3) include acetonitrile, acrylonitrile, propionitrile, glycolonitrile, butyronitrile, cyanobutadiene, succinonitrile, valeronitrile, isovaleronitrile, and benzonitrile. ..
Specific examples of the nitrogen-containing compound of the formula (4) include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, butyl isocyanate, tert-butyl isocyanate, phenyl isocyanate, hexyl isocyanate, benzyl isocyanate, o-toluyl isocyanate, p- Toluyl isocyanate, m-toluyl isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, 4,4'-diisocyanato-3,3'-
Dimethylbiphenyl, dicyclohexylmethane 4,4'-diisocyanate, 4,4'-methylenediphenyl diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 1,5-diisocyanatonaphthalene, m-xylyl Examples include diisocyanate and 3,4-dichlorophenyl isocyanate.

2-3. Characteristics of nitrogen compound and effect on reaction It is not clear why GBL can be obtained in high yield in the present invention, but it is presumed as follows.
General nitrogen compounds have strong basicity and coordinate more strongly to hydrogenation catalysts than succinic acids to inhibit hydrogenation of succinic acids on hydrogenation catalysts, and in complex catalysts, by acid-base bonds. Often neutralizes acidic ligands, again reducing the activity of the hydrogenation catalyst.
However, since the specific nitrogen-containing compound used in the method of the present invention has the above-described specific structure, the basicity is relaxed, so that the specific nitrogen-containing compound is neutral to weakly basic and also has a coordination power to the hydrogenation catalyst. Since the neutralizing effect of the acidic ligand of the complex catalyst also becomes mild, it is considered that these drawbacks are covered and rather contribute to stabilization of the catalytic activity.

The nitrogen compound used in the present invention has the above-mentioned specific structure, molecular weight and the like, and in particular, its vapor pressure at room temperature is 1×10 ⁻¹⁰ Pa or more, more preferably 1×10 ⁻⁹ Pa. The above is preferable. If the vapor pressure of the nitrogen-containing compound at room temperature is less than 1×10 ⁻¹⁰ Pa, the nitrogen-containing compound is less likely to volatilize, which hinders evaporation of GBL and a solvent and makes purification of GBL difficult. The upper limit of the vapor pressure of the nitrogen-containing compound at atmospheric pressure is preferably 1000 Pa or less, more preferably 500 Pa or less. If the vapor pressure of the nitrogen-containing compound at room temperature is too high, the nitrogen-containing compound may volatilize during the hydrogenation reaction, and the effect of stabilizing the hydrogenation catalyst by the nitrogen-containing compound may become insufficient.

Further, the boiling point of the nitrogen compound used in the present invention is preferably 100° C. or higher under normal pressure, more preferably 150° C. or higher. When the boiling point is lower than 100° C., the nitrogen-containing compound is likely to be volatilized during the hydrogenation reaction, as described regarding the vapor pressure. The upper limit of the boiling point of the nitrogen-containing compound is not particularly limited, and is, for example, 700° C. or lower, preferably 600° C. or lower, and is generally used at the decomposition temperature of the nitrogen-containing compound or lower. If the boiling point is too high, the evaporation of GBL and the solvent may be hindered and purification of GBL may be difficult, as in the case where the vapor pressure is too low.
When using a plurality of nitrogen-containing compounds, at least one of them preferably satisfies the above boiling point range.
Table 1 shows the boiling points of typical nitrogen-containing compounds at normal pressure and the vapor pressure at normal temperature.

2-4. Concentration of nitrogen compound and control method thereof The content of the nitrogen-containing compound in the reaction mixture in the production method of the present invention in terms of nitrogen atom is 1 mass ppm or more and less than 5000 mass ppm. The nitrogen atom-containing content of the nitrogen-containing compound is preferably 5 mass ppm or more and less than 3000 mass ppm, more preferably 10 mass ppm or more and less than 1000 mass ppm.

If this concentration is too high, the nitrogen-containing compound coordinates with the hydrogenation catalyst to inhibit the hydrogenation of succinic acids on the hydrogenation catalyst, or neutralize the acidic ligands of the complex catalyst to neutralize the hydrogenation catalyst. May decrease the activity of the hydrogen peroxide, deteriorate the hydrogenation catalyst, and reduce the yield of GBL.
On the other hand, if the concentration of the nitrogen-containing compound is too low, many of the coordination sites of the catalyst metal become empty, the active sites are exposed and the catalyst is apt to deteriorate, and especially the succinic acids obtained by the bio method are When used, it is not economically advantageous because it requires a purification step such as activated carbon treatment or ion exchange treatment in order to reduce the concentration of the nitrogen-containing compound.

Usually, the succinic acids obtained by the bio method include nitrogen-containing compounds that are present in the biomass, are mixed in the fermentation process, or remain unremoved in the purification process of the succinic acids. .. These nitrogen-containing compounds can be used as they are as the nitrogen-containing compound in the method of the present invention, but depending on the content, it may be necessary to reduce the content of the nitrogen-containing compound. As a method therefor, general purification methods such as distillation, filtration and crystallization can be applied.

Since the succinic acids produced by the petrochemical method generally have a very high purity, the above-mentioned specific nitrogen-containing compound may be added in a predetermined amount to the raw material succinic acids, if necessary.
When the above nitrogen-containing compound is present in an amount within a predetermined range, it is possible to prevent deterioration of the metal catalyst, which is the hydrogenation catalyst, while maintaining the GBL yield. Therefore, it is high in the method for producing GBL using the metal catalyst. Continuous operation with stable yield becomes possible.

The concentration of the nitrogen-containing compound can be measured by using gas chromatography, a GC-MS analyzer in combination with this and a mass spectrometer, or a nitrogen content analyzer using a combustion/chemical reduced pressure emission method.
When the concentration of the nitrogen-containing compound in the reaction mixture exceeds the above range, for example, taking the continuous process of (4.) described below as an example,
i) A large amount of high boiling point components are discharged out of the system in the circulation process,
ii) Nitrogen-containing compounds in the circulating liquid are separated by distillation or cation exchange resin,
iii) Using succinic acids containing a lower concentration of nitrogen-containing compound as a raw material,
iv) dilute the reaction system by adding purified lactone or solvent,
By using such a method as described above, it is possible to return to a predetermined concentration range.

On the other hand, when the concentration is below the concentration range specified in the present application, similarly, taking the continuous process of (4.) as an example,
i) Reduce the amount of high boiling point components discharged from the system in the circulation process,
ii) adding a nitrogen-containing compound to the reaction system,
iii) Using succinic acids containing a higher concentration of nitrogen-containing compound as a raw material,
iv) the solvent is distilled off to concentrate the reaction system,
Etc. may be used.

3. Hydrogenation reaction 3-1. Catalyst As the hydrogenation catalyst that can be used for hydrogenating succinic acids, those containing at least one metal selected from transition metals belonging to Groups 8 to 11 of the periodic table are preferable. Examples of the Group 8 to 11 transition metals include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver and gold, and ruthenium, copper and palladium are preferable in terms of catalytic activity. Especially, copper and ruthenium which have high catalytic activity are preferable. The form of the catalyst may be either a solid catalyst or a complex catalyst, but the complex catalyst is preferable in order to obtain higher quality GBL.

3-2. Solid Catalyst As the solid catalyst, the compound containing the above metal may be used as it is, or the metal may be supported on a carrier and used.
When a carrier is used, the carrier is preferably carbon, alumina, silica, silica-alumina, silica-titania, titania, titania-alumina, barium sulfate, calcium carbonate, strontium carbonate, or a combination thereof. The shape of the carrier is not particularly limited, such as powder, granules, and pellets. The use of the carrier is preferable because it is efficient because the odorous components/coloring components and organic impurities in the raw material succinic acid can be adsorbed and removed at the same time. The amount of metal supported is usually 0.1 to 10% by weight of the carrier.

Such a supported catalyst uses, as a metal component, at least one metal of Groups 8 to 11 of the periodic table, for example, copper, palladium, platinum, iridium, rhodium, nickel, rhenium, ruthenium, etc., and uses it as a carrier. Any combination of alumina, silica, carbon, titania and the like with each metal component may be selected in consideration of use conditions and strength.
Preferred supported catalysts include, for example, alumina supported copper oxide, silica supported copper oxide, carbon supported ruthenium, alumina supported ruthenium, carbon supported palladium, alumina supported palladium, titania supported palladium, carbon supported platinum, alumina supported platinum, carbon supported rhodium, And alumina-supported rhodium.

3-3. Complex catalyst A complex catalyst is formed from a catalytic metal and a ligand that coordinates with the catalytic metal.
Hereinafter, a complex catalyst using ruthenium as a metal component as the complex catalyst will be described as an example.
As the raw material for the metal component, both metal ruthenium and ruthenium compounds can be used.

As the ruthenium compound, oxides, hydroxides, inorganic acid salts, organic acid salts, complex compounds and the like can be used. Examples thereof include ruthenium dioxide, ruthenium tetroxide, ruthenium dihydroxide, ruthenium chloride, ruthenium bromide and iodide. Ruthenium, ruthenium nitrate, ruthenium acetate, and other ruthenium oxides, ruthenium hydroxides and ruthenium salts, sodium hexachlororuthenate, dipotassium tetracarbonylruthenate, didecium octadecacarbonylhexaruthenate, undecacarbonylhydridotriruthenate tetraphenylphos Ruthenium salts such as phonium, pentacarbonylruthenium, tris(acetylacetonato)ruthenium, cyclopentadienyldicarbonylruthenium, dibromotricarbonylruthenium, chlorotris(triphenylphosphine)hydridolthenium, tetra(triphenylphosphine)di Examples include ruthenium complexes such as hydridoruthenium, tetra(trimethylphosphine)dihydridoruthenium, bis(tri-n-butylphosphine)tricarbonylruthenium, tetrahydridododecacarbonyltetraruthenium, and dodecacarbonyltriruthenium. Ruthenium chloride, tris(acetylacetonato)ruthenium, and ruthenium acetate, which are easily available, are preferably used.

The ligand of the ruthenium complex catalyst used in the method of the present invention is preferably a phosphorus ligand. As the phosphorus ligand, those having an aryl group such as triphenylphosphine, diphenylmethylphosphine and dimethylphenylphosphine can also be used, but trialkylphosphine, especially trialkyl in which a phosphorus atom is bonded to a primary alkyl group Phosphine or its decomposition product is preferable. This alkyl group may have another substituent.

The carbon number of the alkyl group of such a trialkylphosphine is preferably about 1 to 12, and it is not necessary that all three alkyl substituents are the same, and all of them may be the same or different. It does not matter if one is the same and one is different.
Examples of the phosphine forming a ligand include tridecanylphosphine, trinonylphosphine, trioctylphosphine, triheptylphosphine, trihexylphosphine, tripentylphosphine, tributylphosphine, tripropylphosphine, triethylphosphine, trimethylphosphine, Dimethyloctylphosphine, dioctylmethylphosphine, dimethylheptylphosphine, diheptylmethylphosphine, dimethylhexylphosphine, dihexylmethylphosphine, dimethylcyclohexylphosphine, dicyclohexylmethylphosphine, dimethylpentylphosphine, dipentylmethylphosphine, dimethylbutylphosphine, dibutylmethylphosphine, tri Heptylphosphine, tricyclohexylphosphine, trihexylphosphine, tripentylphosphine, tribenzylphosphine, 1,1,2,2-dimethylphosphinoethane, 1,1,2,2-dimethylphosphinopropane, 1,1,2 , 2-dimethylphosphinobutane, 1,1,2,2-dioctylphosphinoethane, 1,1,2,2-dioctylphosphinopropane, 1,1,2,2-dioctylphosphinobutane, 1,1 2,2-dihexylphosphinoethane, 1,1,2,2-dihexylphosphinopropane, 1,1,2,2-dihexylphosphinobutane, 1,1,2,2-dibutylphosphinoethane, 1 1,2,2-dibutylphosphinopropane, 1,1,2,2-dibutylphosphinobutane, 1,1-diphosphinane, 1,4-dimethyl-1,4-diphosphane, 1,3-dimethylphosphory Nan, 1,4-dimethylphosphorinane, 8-methyl-8-phosphinobicyclooctane,
Examples thereof include phosphines such as 4-methyl-4-phosphatetracyclooctane, 1-methylphosphorane, and 1-methylphosphonan, and their shapes are also monodentate ligands, bidentate ligands, and cyclic ligands. Both are used.

Further, as the phosphorus ligand, not only the above phosphine but also phosphite, phosphinate, phosphine oxide, aminophosphine, phosphinic acid and the like can be used.
The amount of these phosphorus ligands used is 0. It is in the range of 1 to 1000 mol, preferably 1 to 100 mol.
Further, the ruthenium complex catalyst for hydrogenating succinic acid may be used in the reaction in the form of a cationic complex by using a conjugate base of an acid having a pKa of less than 2, for improving the activity, stabilizing the catalyst, and the like. It is preferable in terms. Such a conjugate base of an acid having a pKa of less than 2 may be any one that forms such a conjugate base during catalyst preparation or in the reaction system. For example, a Bronsted acid having a pKa of less than 2 or various kinds thereof can be used. Salt or the like is used.

Acids and salts thereof that can be used for such purposes include nitric acid, perchloric acid, borofluoric acid, hexafluorophosphoric acid, inorganic acids such as fluorosulfonic acid, trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, Bronsted acids such as organic acids such as dodecyl sulfonic acid, octadecyl sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid, paratoluene sulfonic acid, tetra(pentafluorophenyl)boronic acid, sulfonated styrene-divinylbenzene copolymer, or the like. Examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and silver salts of these acids.

Further, the conjugate base of the above acid may be added in the form of an acid derivative which is considered to be produced in the reaction system. Similar effects can be expected even when added to the reaction system in the form of, for example, an acid halide, an acid anhydride, or an ester.
The amount of these acids or salts thereof used is 1000 mol or less, preferably 100 mol or less, with respect to the ruthenium metal. It is particularly preferably 10 mol or less.

3-4. Solvent The production of gamma-butyrolactone by the method of the present invention can be carried out using the reaction raw materials and the reaction product mixture as a solvent, but various solvents can also be used within a range that does not inhibit the purpose or progress of the reaction.
Examples of such a solvent include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether and dioxane; alcohols such as methanol, ethanol, n-butanol, benzyl alcohol, phenol, ethylene glycol and diethylene glycol; formic acid, Carboxylic acids such as acetic acid, propionic acid and toluic acid; Esters such as methyl acetate, butyl acetate and benzyl benzoate; Aromatic hydrocarbons such as benzene, toluene, ethylbenzene and tetralin; n-hexane, n-octane, cyclohexane Aliphatic hydrocarbons such as; Halogenated hydrocarbons such as dichloromethane, trichloroethane and chlorobenzene; Sulfones such as dimethyl sulfone; Sulfoxides such as dimethyl sulfoxide; Lactones such as caprolactone; Polyethers such as tetraglyme and triglyme Carbonic acid esters such as dimethyl carbonate and ethylene carbonate, and the like, preferably ethers, polyethers, and lactones.

3-5. Reaction Conditions The hydrogenation reaction carried out by the method of the present invention may be continuous or batchwise. The reaction temperature is generally 50 to 250°C, preferably 100 to 250°C, more preferably 150 to 220°C. The hydrogen partial pressure in the reaction system is not particularly limited, but industrially it is usually 0.01 to 10 MPa·G (gauge pressure), preferably 0.03 to 5 MPa·G.

From the reaction product solution, GBL, which is the target product, can be separated by usual separation means such as distillation and extraction.
The water content in the reaction system is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass. If the water content is too high, the equilibrium between succinic acid and its anhydride shifts to the succinic acid side, so the concentration of succinic anhydride tends to decrease, and the GBL generation rate tends to decrease. On the other hand, if the water content is too low, the concentration of succinic acid serving as the counter anion of the ruthenium catalyst decreases, and the cationic property of the catalyst decreases, so that the hydrogenation reaction activity of the catalyst tends to decrease.
As a method for removing water from the reaction system, a gas stripping method or the like can be used, and depending on the reaction process, water may be distilled off by distillation or a dehydrating agent may be added. When hydrogen is used as the gas for gas stripping, it is efficient because the succinic acids can be converted into GBL simultaneously with the removal of water in the reaction solution.

4. Example of industrial process to which the method of the present invention is applied The present invention can be suitably applied to a continuous reaction process including a hydrogenation step, a purification step, and a circulation step. In this case, in order to stably maintain the range of the content (concentration) of the nitrogen-containing compound specified by the method of the present invention, a part of the circulating liquid containing the nitrogen-containing compound is discharged out of the system, and a part of it is reacted. By circulating through the system, the concentration of the nitrogen-containing compound in the reaction mixture can be controlled.

The GBL obtained by the reaction method of the present invention can be obtained as a highly purified GBL by performing a general purification method such as extraction, distillation and crystallization after the completion of the reaction. If a higher degree of purification is required, it may be further purified with an ion exchange resin.
In the method of the present invention, it is preferable to circulate the residual liquid containing the hydrogenation catalyst after separating the product GBL (hereinafter sometimes referred to as “catalyst liquid”) to the reaction process by the above-mentioned circulation process.

As the component to be circulated, in addition to the active component such as catalyst and unreacted succinic acid medium, a solvent or other component may be contained as long as it does not adversely affect the reaction step, but a component having a higher boiling point than the target product. Is preferably circulated.
For example, when at least a part of the high boiling point component containing the catalyst separated from the GBL in the distillation column after the hydrogenation reaction step is circulated to the reaction step, the nitrogen-containing compound contained in the reaction raw material is also a high boiling point component. As a result, it circulates along with the catalyst and accumulates in the process. Therefore, in order to keep the concentration of the nitrogen-containing compound in the reaction mixture within the concentration range specified in the present invention, usually, a part of the high boiling point component containing the nitrogen-containing compound is discharged (purged) out of the system. Will be required.

There is no particular limitation on the method of purging the high boiling point component out of the system.For example, the catalyst liquid in which the high boiling point component is accumulated is used as the high boiling point component-containing liquid in the refining step, and a part thereof is purged out of the system. Good.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
1. Raw materials succinic acid, succinic acid diamide, succinic acid monoamide: special grade reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Triglyme: Reagent first grade (Wako Pure Chemical Industries, Ltd., reagent first grade)
Trioctylphosphine: (manufactured by Wako Chemical Co., Ltd.)
Tris(acetylacetonato)ruthenium: (NE Chemcat Corporation)

2. Analysis method [Gas chromatography analysis]
GBL was analyzed with a gas chromatography analyzer (GC-17A manufactured by Shimadzu Corporation) using a DB-1 column (nonpolar) manufactured by Agilent.
[Inductively coupled plasma optical emission spectrometry (ICP-OES)]
Ru analysis was carried out by an organic solvent direct introduction method using an ICP emission spectrometer (iCAP6500Duo manufactured by Thermo Scientific Co., Peltier-cooled organic solvent introduction system).
[Absorbance analysis]
The sample was put in a 10 mm quartz cell, and the absorbance at a wavelength of 315 nm was measured with a spectrophotometer (UV-2000 type manufactured by Hitachi High-Technologies Corporation).

3. Examples and Comparative Examples <Reference Example 1>
5.0 g (Ru) of succinic acid 5.9 g (11.8% by mass) and a ruthenium complex having trioctylphosphine as a ligand dissolved in triglyme in an autoclave (material: SUS316) having an internal capacity of 100 ml. : 400 mass ppm), and 39.1 g of triglyme as a solvent. The nitrogen compound concentration in the reaction mixture was less than 1 mass ppm.

After the magnetic rotary stirrer was put into the autoclave, the inside of the system was sufficiently replaced with hydrogen. The temperature was raised with stirring using a magnetic stirrer, and hydrogen was injected under pressure so that the internal pressure became 0.9 MPa·G (gauge pressure) when the internal temperature of the autoclave reached 205°C. At this time, the reaction was started, and then the hydrogenation reaction was carried out for 2 hours.
After the reaction was completed, a part of the obtained reaction product liquid was collected and analyzed by gas chromatography. As a result, the yield of gammabutyrolactone was 29.6%. The reaction results are shown in Table 2.

<Example 1>
In addition to the raw materials of Reference Example 1, the autoclave was charged with 0.2540 g of succinic diamide (nitrogen atom content: 1223 mass ppm) to carry out a hydrogenation reaction in the same manner as in Example 1, The obtained reaction product liquid was analyzed.
The gamma butyrolactone yield was 30.0%. The reaction results are shown in Table 2.

<Example 2>
A hydrogenation reaction was carried out in the same manner as in Example 1 except that 0.2505 g of succinic acid diamide (nitrogen atom content: 1211 mass ppm) was charged in the autoclave in addition to the raw materials of Reference Example 1. The obtained reaction product solution was analyzed. The reaction results are shown in Table 2.
<Example 3>
In addition to the raw materials of Reference Example 1, the same as Example 1 except that 0.1 g (nitrogen atom content: 412 mass ppm) of 2,3,5,6-tetramethylpyrazine was charged in the autoclave. The hydrogenation reaction was carried out, and the obtained reaction product solution was analyzed. The reaction results are shown in Table 2.

<Comparative Example 1>
In addition to the raw materials of Reference Example 1 above, a hydrogenation reaction was carried out in the same manner as in Example 1 except that 2.5041 g (nitrogen atom content: 12112 mass ppm) of succinic acid diamide was charged in the autoclave. The obtained reaction product solution was analyzed. The reaction results are shown in Table 2.
<Comparative example 2>
A hydrogenation reaction was carried out in the same manner as in Example 1 except that 2.5015 g (nitrogen atom content: 5986 mass ppm) of succinic acid monoamide was charged in the autoclave in addition to the raw materials of Reference Example 1. The obtained reaction product solution was analyzed. The reaction results are shown in Table 2.

<Comparative example 3>
In addition to the raw materials of Reference Example 1, the same as Example 1 except that 1.5 g (nitrogen atom content: 6176 mass ppm) of 2,3,5,6-tetramethylpyrazine was charged in the autoclave. The hydrogenation reaction was carried out, and the obtained reaction product solution was analyzed. The reaction results are shown in Table 2.

<Example 4>
A solution of a ruthenium complex having trioctylphosphine as a ligand dissolved in triglyme was added to 0.25 g (Ru 2000 mass ppm), 0.8 mg of succinic acid diamide (nitrogen atom content: 19 mass ppm) and 9 g of a solvent triglyme. A mixed solution of 0.75 g was prepared. When these solutions were stored for 72 hours in an open state in a 100 mL glass vial in the air, the solution which was pale yellow before storage was discolored to pale red. The amount of change in the absorbance of the obtained solution at 315 nm was 0.23.

<Example 5>
When stored in the atmosphere in the same manner as in Example 4 except that the amount of succinic acid diamide used was 3.0 mg (nitrogen atom content: 72 mass ppm), the color changed to pale red. Table 3 shows the measurement results of the absorbance. 45 g of this discolored catalyst and 5 g of succinic acid were mixed to prepare a hydrogenation raw material. A hydrogenation reaction was carried out for 3 hours in the same manner as in Reference Example 1 except for the above, and after completion of the reaction, the obtained reaction product solution was analyzed in the same manner as in Reference Example 1, and as a result, the yield of gammabutyrolactone was 24.0%. Met. The reaction results are shown in Table 3.

<Comparative example 4>
When stored in the air in the same manner as in Example 4, except that succinic acid diamide was not added (nitrogen atom content in the system: less than 1 mass ppm), the color changed to red. Table 3 shows the measurement results of the absorbance. 45 g of this discolored catalyst and 5 g of succinic acid were mixed to prepare a hydrogenation raw material. A hydrogenation reaction was carried out for 3 hours in the same manner as in Reference Example 1 except for the above, and after the completion of the reaction, the obtained reaction product solution was analyzed in the same manner as in Reference Example 1, and as a result, the yield of gammabutyrolactone was 18.0%. Met. The reaction results are shown in Table 3.

4. Evaluation of Results (1) By comparing Examples 1, 2 and 3 shown in Table 2 with Comparative Examples 1, 2 and 3, Examples in which the concentration of the nitrogen-containing compound during the hydrogenation reaction was within the predetermined range of the present application , The GBL yield was at the same level as that of the reference example (raw material containing no nitrogen-containing compound), while the yield was remarkably reduced in Comparative Examples 1, 2 and 3 in which this concentration exceeded the range of the present application. You can see that
(2) In Example 5 of Table 3, the addition of the nitrogen-containing compound reduces the degree of change in the absorbance at a wavelength of 315 nm, resulting in a high GBL yield. On the other hand, in Comparative Example 4, the stability of the catalyst was lowered probably because the concentration was below the range specified in the present application, and the absorbance at the wavelength of 315 nm was significantly changed, and the GBL yield was low.
From the above results, the effect of the present invention is clear.

When using the method of producing gamma-butyrolactone, which is useful as a reaction intermediate for industrial solvents, detergents, and polymer chemicals, by hydrogenating succinic acids in the presence of a catalyst, it is possible to reduce catalyst deterioration and produce a stable and efficient production. Is possible. The method of the present invention is particularly effective when a biomethod with a small environmental load is adopted.

Claims (8)

In the method for producing gamma-butyrolactone by hydrogenating succinic acid and/or its derivative (hereinafter, both may be collectively referred to as "succinic acids"), a nitrogen-containing nitrogen contained in the reaction mixture during the hydrogenation reaction. The total content of the compounds is 70 mass ppm or more and less than 1500 mass ppm in terms of nitrogen atom, and the nitrogen-containing compound is at least a neutral to weakly basic molecular weight of 1000 or less represented by the following general formula (1). A method for producing gamma-butyrolactone, which is either an amide compound or 2,3,5,6-tetramethylpyrazine.

(In the formula (1), R ¹ and R ³ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, a hydroxy group, an alkylthio group, an arylthio group, an alkylcarbonyl group, or an arylcarbonyl group. Represents a group, and these groups may further have a substituent, and the substituent may contain a hetero atom, and R ¹ and R ³ may be the same or different. Provided that the total number of carbon atoms of R ¹ and R ³ is 50 or less, and the case where all of R ¹ and R ³ are hydrogen atoms is excluded, R ² represents an alkylcarbonyl group or an arylcarbonyl group, these groups may further have a substituent.) The method for producing gamma-butyrolactone according to claim 1, wherein the nitrogen-containing compound has a molecular weight of 200 or less. The production of gammabutyrolactone according to claim 1 or 2, wherein the hydrogenation reaction is carried out using a catalyst containing at least one metal selected from transition metals belonging to Groups 8 to 11 of the periodic table. Method. 4. The method for producing gamma-butyrolactone according to claim 1, wherein the nitrogen-containing compound has a vapor pressure at room temperature (25° C.) of 1×10 ⁻¹⁰ Pa or more and 1000 Pa or less. .. The said hydrogenation reaction is performed using the catalyst containing ruthenium or copper, The manufacturing method of the gamma butyrolactone of any one of Claims 1-4 characterized by the above-mentioned. The method for producing gamma-butyrolactone according to any one of claims 1 to 5, wherein the hydrogenation reaction is performed by using a ruthenium complex having a tertiary organic phosphorus compound as a ligand as a catalyst. The method for producing gamma-butyrolactone according to claim 1, wherein the succinic acids are produced by a fermentation method using a biomass raw material. The succinic acid is succinic acid, the nitrogen-containing compound is at least one compound selected from the group consisting of succinic acid diamide, succinic acid monoamide, succinimide, and the catalyst used in the hydrogenation reaction is It is a ruthenium complex which has a tertiary organic phosphorus compound as a ligand, The manufacturing method of the gamma butyrolactone of any one of Claims 1-7 characterized by the above-mentioned.